EP0276503A1 - Verfahren zur Herstellung eines 2-Alkyl- oder 2-Phenyl-1,4,5,6-tetrahydropyrimidins und Verfahren zur Herstellung von 2-Alkyl- oder 2-Phenyl-pyrimidinen - Google Patents

Verfahren zur Herstellung eines 2-Alkyl- oder 2-Phenyl-1,4,5,6-tetrahydropyrimidins und Verfahren zur Herstellung von 2-Alkyl- oder 2-Phenyl-pyrimidinen Download PDF

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Publication number
EP0276503A1
EP0276503A1 EP87202466A EP87202466A EP0276503A1 EP 0276503 A1 EP0276503 A1 EP 0276503A1 EP 87202466 A EP87202466 A EP 87202466A EP 87202466 A EP87202466 A EP 87202466A EP 0276503 A1 EP0276503 A1 EP 0276503A1
Authority
EP
European Patent Office
Prior art keywords
acid
alkyl
tetrahydropyrimidine
group
diaminopropane
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP87202466A
Other languages
English (en)
French (fr)
Other versions
EP0276503B1 (de
Inventor
Antonius Jacobus Josephus Maria Teunissen
Willem Klop
Hubertus Johannes Aloysius Victor Delahaye
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Koninklijke DSM NV
Original Assignee
Stamicarbon BV
DSM NV
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Stamicarbon BV, DSM NV filed Critical Stamicarbon BV
Priority to AT87202466T priority Critical patent/ATE78471T1/de
Publication of EP0276503A1 publication Critical patent/EP0276503A1/de
Application granted granted Critical
Publication of EP0276503B1 publication Critical patent/EP0276503B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/06—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/26—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms

Definitions

  • the invention relates to a process for preparing a 2-alkyl-1,4,5,6-tetrahydropyrimidine with the formula where R represents a straight or branched chain with 1-8 C-atoms or a phenyl group from 1,3-diaminopropane and an alkanecarboxylic acid, in which the alkyl group of such an acid is the same as the R group described above.
  • the process according to the invention for preparing a 2-alkyl-1,4,5,6-tetrahydropyrimidine with the formula where R represents a straight or branched chain with 1-8 C-atoms or a phenyl group from 1,3-diaminopropane and an alkanecarboxylic acid, in which the alkyl group of such an acid is the same as the R group described above, is characterized in that the starting materials are reacted in the gas phase in the presence of an oxide catalyst at a temperature of between 250 and 450 ⁇ C and from the reaction mixture thus obtained the 2-alkyl-1,4,5,6-tetrahydropyrimidine is recovered.
  • the advantage of the process according to the invention is that the preparation takes place in one step.
  • the process according to the invention can in principle be carried out con­tinuously in a simple manner, which constitutes a cost advantage, in part because no further processing of the linear product of conden­sation need be carried out between two steps.
  • 2-hydroxy-1,3-diaminopropane can be used as starting material as well.
  • the resulting reaction product is the 2-alkyl-5-hydroxy-1,4,5,6-tetrahydropyrimidine.
  • alkanecarboxylic acid is used in the process according to the invention depends on what alkyl group is desired in the end product. If, for instance, 2-t.butyl-1,4,5,6-tetrahydropyrimidine is to be prepared, pivalic acid is started from. If the 2-methyl analogon is to be prepared, acetic acid will be started from. Generally, alka­necarboxylic acids with the formula R-COOH can be started from, in which the R group can be found back as alkyl group at the 2-site in the end product. This R group generally contains 1-8 C atoms and may be aliphatic, as well as aromatic.
  • Suitable acids are, for instance, acetic acid, propionic acid, pivalic acid, (iso)-butyric acid and ben­zoic acid.
  • alkanecarboxylic acid is in this connection understood also to mean an ester, anhydride and/or an acid halide of such an acid, such as, for instance, the C 1-4 alkylesters of the above-mentioned acids, as well as the acid chlorides and acid bromides of those acids.
  • the process according to the invention is carried out in the gas phase.
  • the temperature may vary within wide limits, for instance between 250 and 450 ⁇ C.
  • the pressure at which the reaction is carried out is of no particular importance as long as the gas phase is main­tained in combination, of course, with the temperature. Generally the process will be carried out at autogenous pressure.
  • a gas for instance nitrogen and/or hydrogen, may be introduced into the reactor in order to make the evaporation proceed evenly.
  • oxide catalysts which must have an oxi­dizing and/or dehydrating effect, are the oxides of elements from groups 3, 4 and/or 5 of the Periodic System. Particularly the oxides of aluminium and zirconium, possibly in combination with phosphoric acid (ester), are important for a high yield.
  • the process according to the invention can advantageously be extended to include the preparation of the corresponding 2-alkylpyrimidines by passing the reaction mixture in the gas phase over a second catalyst bed after the formation of the 2-alkyl-1,4,5,6-tetrahydropyrimidine without removal of water between times.
  • This second catalyst must have a dehydrogenating activity.
  • the customary supported catalysts are eligible such as, for instance, those of group 8 of the Periodic System.
  • the second catalyst system used is preferably palladium on alumina. These catalysts generally contain 0.1-10% (wt) palladium, preferably 0.5-5% (wt), calculated on the total catalyst. Also an alkali metal may be added to the catalyst in amounts ranging between 0.01 and 2% (wt) calculated on the total catalyst.
  • the dehydrogenation catalyst can be applied on a carrier known per se.
  • Such carriers may contain, for instance, alumina, carbon and silicon oxide.
  • the modes of realizing gas phase reactions known per se are eligible, for instance the mode of realization in which the gaseous starting mixture is passed over the catalyst in the form of a fixed bed or a so-called fluid bed.
  • the space velocity can be varied, for instance between 0.01 and 10g starting compound per millilitre cata­lyst material (bulk volume) per hour.
  • the further processing of the 2-alkyl-1,4,5,6-tetrahydropyrimidine obtained in the reaction can be effected in a manner known per se by cooling and by, for instance, subsequent distillation or extraction.
  • the 2-alkyl-1,4,5,6-tetrahydropyrimidines obtained in the pro­cess according to the invention can be used as intermediates for the preparation of the corresponding pyrimidines, which in their turn can be used as intermediates for crop protection agents.
  • 1,3-diaminopropane and pivalic acid trimethylacetic acid
  • a vertical tubular reactor length 400 mm, diameter 20 mm
  • This catalyst consisted of 98% zirconium oxide and 2% aluminium oxide.
  • the grain size of the catalyst was 3-4 mm.
  • the pivalic acid metering pump, the metering vessel and the feed and outlet pipes were heated to a temperature of 60 ⁇ C.
  • the acid was metered at a rate of 8.16 grammes per hour.
  • the metering velocity of 1,3-diaminopropane was 5.92 grammes per hour.
  • the yield of 2-t.butyl-1,4,5,6-tetrahydropyrimidine was calculated on the basis of the amount of 2-t.butyl-1,4,5,6-tetrahydropyrimidine in the reaction product calculated on the amount of pivalic acid metered.
  • 2-phenyl-1,4,5,6-tetrahydropyrimidine was prepared from 1,3-diaminopropane and benzoic acid in a molar ratio of 2:1. After three hours the yield of 2-phenyl-1,4,5,6-tetrahydropyrimidine was 70% calculated on benzoic acid.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Catalysts (AREA)
EP87202466A 1986-12-12 1987-12-09 Verfahren zur Herstellung eines 2-Alkyl- oder 2-Phenyl-1,4,5,6-tetrahydropyrimidins und Verfahren zur Herstellung von 2-Alkyl- oder 2-Phenyl-pyrimidinen Expired - Lifetime EP0276503B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT87202466T ATE78471T1 (de) 1986-12-12 1987-12-09 Verfahren zur herstellung eines 2-alkyl- oder 2- phenyl-1,4,5,6-tetrahydropyrimidins und verfahren zur herstellung von 2-alkyl- oder 2-phenyl- pyrimidinen.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
NL8603168 1986-12-12
NL8603168A NL8603168A (nl) 1986-12-12 1986-12-12 Werkwijze voor de bereiding van een 2-alkyl-1,4,5,6-tetrahydropyrimidine.

Publications (2)

Publication Number Publication Date
EP0276503A1 true EP0276503A1 (de) 1988-08-03
EP0276503B1 EP0276503B1 (de) 1992-07-22

Family

ID=19848993

Family Applications (1)

Application Number Title Priority Date Filing Date
EP87202466A Expired - Lifetime EP0276503B1 (de) 1986-12-12 1987-12-09 Verfahren zur Herstellung eines 2-Alkyl- oder 2-Phenyl-1,4,5,6-tetrahydropyrimidins und Verfahren zur Herstellung von 2-Alkyl- oder 2-Phenyl-pyrimidinen

Country Status (8)

Country Link
US (1) US4880929A (de)
EP (1) EP0276503B1 (de)
JP (1) JPS63156780A (de)
AT (1) ATE78471T1 (de)
DE (1) DE3780616T2 (de)
ES (1) ES2033816T3 (de)
GR (1) GR3006051T3 (de)
NL (1) NL8603168A (de)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0342742A1 (de) * 1988-05-16 1989-11-23 DowElanco Verfahren zur Herstellung von 2-Alkylpyrimidine

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3820176A1 (de) * 1987-12-18 1989-06-29 Bayer Ag Verfahren zur herstellung von phosphorsaeurederivaten und zwischenprodukten
CA2023492A1 (en) * 1989-08-31 1991-03-01 Barry Clifford Lange Herbicidal glutarimides
US5180700A (en) * 1991-05-13 1993-01-19 Dowelanco Regeneration and extension of lifetime of dehydrogenation catalysts used in the preparation of 2-alkylpyrimidines
US5189166A (en) * 1992-07-17 1993-02-23 Dowelanco Process for the preparation of 2-alkyl-5-hydroxypyrimidines from 1,3-diamino-2-propanol and an alkanecarboxylic acid

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3041338A (en) * 1958-07-21 1962-06-26 Nalco Chemical Co 5-hydroxy substituted tetrahydro-pyrimidines
US3050523A (en) * 1960-01-08 1962-08-21 Air Prod & Chem Preparation of pyrimidines
EP0117882A1 (de) * 1981-09-14 1984-09-12 The Dow Chemical Company Aminopropylpivalamide und Verfahren zur Herstellung
EP0193973A1 (de) * 1983-03-04 1986-09-10 The Dow Chemical Company Verfahren zur Herstellung von 2-Alkylpyrimidin durch Dehydrierung von 2-Alkyltetrahydropyrimidin

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2704757A (en) * 1954-01-13 1955-03-22 Searle & Co 5-hydroxy-3, 4, 5, 6-tetrahydropyriminines
US4376201A (en) * 1981-09-14 1983-03-08 The Dow Chemical Company Preparation of 2-alkylpyrimidines
NL8403258A (nl) * 1984-10-26 1986-05-16 Stamicarbon Werkwijze voor de bereiding van pyrimidine.
NL8502797A (nl) * 1985-02-15 1986-09-01 Stamicarbon Werkwijze voor de bereiding van 2-alkylpyrimidine.

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3041338A (en) * 1958-07-21 1962-06-26 Nalco Chemical Co 5-hydroxy substituted tetrahydro-pyrimidines
US3050523A (en) * 1960-01-08 1962-08-21 Air Prod & Chem Preparation of pyrimidines
EP0117882A1 (de) * 1981-09-14 1984-09-12 The Dow Chemical Company Aminopropylpivalamide und Verfahren zur Herstellung
US4493929A (en) * 1981-09-14 1985-01-15 The Dow Chemical Company Preparation of 2-alkylpyrimidines
EP0193973A1 (de) * 1983-03-04 1986-09-10 The Dow Chemical Company Verfahren zur Herstellung von 2-Alkylpyrimidin durch Dehydrierung von 2-Alkyltetrahydropyrimidin

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, vol. 85, 1976, pages 462-463, abstract no. 142251m, Columbus, Ohio, US; J. OKADA et al.: "Formation of 2-ethylpyrimidine from trimethylenediamine over platinum group metal-aluminum oxide catalysts and its kinetics study", & YAKUGAKU ZASSHI 1976, 96(6), 801-9 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0342742A1 (de) * 1988-05-16 1989-11-23 DowElanco Verfahren zur Herstellung von 2-Alkylpyrimidine

Also Published As

Publication number Publication date
DE3780616D1 (de) 1992-08-27
ES2033816T3 (es) 1993-04-01
EP0276503B1 (de) 1992-07-22
DE3780616T2 (de) 1993-03-04
NL8603168A (nl) 1988-07-01
ATE78471T1 (de) 1992-08-15
US4880929A (en) 1989-11-14
GR3006051T3 (de) 1993-06-21
JPS63156780A (ja) 1988-06-29

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